JP6744420B2 - Method for producing etched glassware - Google Patents

Description

The present invention relates to a selective etching process of glass, for example for decorative purposes, and more particularly to a glass etching process using ink jet techniques.

A preferred, selective chemical etching method for obtaining a specific pattern on the surface of glassware is to use a protective mask that is resistant to the etching process to etch only certain parts of the glass surface. Allows for exposure. Then, after the etching process, the protective mask is removed. The resulting etched pattern is therefore a negative of the previously applied protective mask.

US Pat. Nos. 5,968,049 (GLAVERBEL) and 2 (AGC) selectively protect a glass surface onto which a protective layer containing a low temperature molten wax is deposited, by screen printing, by a hot applicator, or by an ink jet technique. The method of etching is disclosed.

Wax deposition by ink jet printing requires heating the printhead to a temperature high enough to melt the wax, which then cools and hardens upon contact with the cooler glass surface. Maintaining the printhead at a relatively high temperature can have a detrimental effect on printhead life.

Another drawback may be the poor stability of ink jet inks containing wax.

In Patent Document 3 (AGC), the protective layer is provided by an ink jet method using a UV curable liquid. UV curable ink jet inks include N-vinyl-caprolactam, acrylate monomers, photoinitiators and glycol ether acrylates.

Spraying and curing of the protective layer occur simultaneously.

The UV light used to cure the jetted protective layer may be reflected from the surface of the glass. Such reflected UV light that reaches the printhead of an ink jet printer can induce clogging of the printhead nozzles.

Another problem that may arise relates to the removal of the protective layer, also called stripping of the protective layer. The protective layer that is removed typically forms flakes in an alkaline stripping bath. The stripping solution is usually a solution of an alkali metal hydroxide such as sodium or potassium hydroxide or an amine-based solution such as mono- or tri-ethanolamine and tetramethylammonium hydroxide. The stripping solution breaks the polymer chains during the polymerization of the resist and at the cross-linking points of the three-dimensional structure formed before the bond between the ink resistant film and the glass surface is broken. To do. In order to extend the working life of the stripping solution, it is necessary to filter the solution to remove the stripped flakes of the ink resistant film. If the flake size is too large, it tends to stick to the stripping equipment and disrupt smooth running of the manufacturing process. If the flakes are too small, they pass through the filter and back into the stripping bath. These small flakes accumulate after a while and start to disrupt the smooth running of the manufacturing process again. These very small flakes tend to block the sprayer nozzles in the stripping line.

The flakes may also redeposit on the surface of the etched glass and, for example, in the etched pattern, necessitating further cleaning steps.

The stripped flake size depends mainly on the type of stripping solution, the concentration of the stripping solution, the temperature of the stripping solution and the design of the stripping device, etc. This many influencing factors make it very difficult to adjust the flake size to the desired size.

International Publication No. 2006/087320 Pamphlet International Publication No. 2009/083468 Pamphlet International publication 2013/189762 pamphlet

It is an object of the present invention to provide an improved process for the production of selectively etched glass products in order to overcome the abovementioned problems.

This object has been realized by the manufacturing method described in claim 1. The aforementioned clogging problem was solved by choosing a specific time interval between jetting of the ink jet ink onto the glassware and curing.

Further advantages and embodiments of the invention will be apparent from the description below.

FIG. 1 illustrates a preferred embodiment for making an etched glass product. First, the UV cured image (2) is printed on the glass surface (1). Then, during the etching process, the glass is etched in the areas not protected by the UV-cured image (3), while keeping the glass surface protected by the UV-cured image substantially intact. After removal of the UV-cured image, an etched glassware (10) is obtained which comprises etched areas (4) and smooth areas (6). FIG. 2 shows another embodiment for producing an etched glass product in which the second side of the glass sheet is completely covered by a UV-curing layer (5) to protect it from the etching solution. Show. FIG. 3 shows a photograph of the etched glass sheet obtained in Example 2.

Detailed Description of the Invention
Definitions For example, the term "monofunctional" in a monofunctional polymerizable compound means that the polymerizable compound contains one polymerizable group.

For example, the term "difunctional" in a difunctional polymerizable compound means that the polymerizable compound contains two polymerizable groups.

For example, the term "multifunctional" in a polyfunctional polymerizable compound means that the polymerizable compound contains three or more polymerizable groups.

The term “alkyl” refers to all possible variants for each number of carbon atoms in an alkyl group, ie methyl, ethyl, n-propyl and isopropyl for 3 carbon atoms; 4 N-butyl, isobutyl and tert-butyl for the carbon atoms of 5 and n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-for the 5 carbon atoms. Means butyl, etc.

Unless otherwise specified, substituted or unsubstituted alkyl groups are preferably C ₁ -C ₆ -alkyl groups.

Unless otherwise specified, the substituted or unsubstituted alkenyl groups are preferably C ₁ -C ₆ -alkenyl groups.

Unless otherwise specified, a substituted or unsubstituted alkynyl group is preferably a C ₁ -C ₆ -alkynyl group.

Unless otherwise specified, the substituted or unsubstituted aralkyl groups are preferably phenyl or naphthyl groups containing ₁ , 2, 3 or 4 or more C ₁ to C ₆ -alkyl groups.

Unless otherwise specified, the substituted or unsubstituted alkaryl groups are preferably C ₇ to C ₂₀ -alkyl groups, including phenyl or naphthyl groups.

Unless otherwise specified, the substituted or unsubstituted aryl group is preferably a phenyl group or a naphthyl group.

Unless otherwise specified, a substituted or unsubstituted heteroaryl group is preferably a 5- or 6-membered ring substituted with 1, 2 or 3 oxygen atoms, nitrogen atoms, sulfur atoms, selenium atoms or combinations thereof. Is.

For example, the term “substituted” in a substituted alkyl group means that the alkyl group may be substituted with atoms other than those atoms normally contained in such groups, ie carbon and hydrogen. For example, the substituted alkyl group may include a halogen atom or a thiol group. Unsubstituted alkyl groups contain only carbon and hydrogen atoms.

Unless otherwise specified, substituted alkyl groups, substituted alkenyl groups, substituted alkynyl groups, substituted aralkyl groups, substituted alkaryl groups, substituted aryl and substituted heteroaryl groups are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl. , Isobutyl and tert-butyl, esters, amides, ethers, thioethers, ketones, aldehydes, sulfoxides, sulfones, sulfonate esters, sulfonamides, -Cl, -Br, -I, -OH, -SH, -CN and -NO. It is replaced by one or more constituents selected from the group consisting of ₂ .

In the present invention, the etching of glass involves the removal of a certain amount of material at the surface of the glass, which imparts a transparent/scattering aspect to the glass, a certain texture and sometimes a roughness. Understood to mean. The term "chemical etching" is used when the removal of material is carried out by a chemical attack/reaction.

Method of Making a Selectively Etched Glass Product According to a preferred embodiment of the present invention, a method of making an etched glass product (10) comprises:
a) jetting the image (2) with a UV curable ink jet ink on the surface of the glass product,
b) UV curing the image (2),
c) etching the surface not covered by the UV cured image (3) to obtain an etched image (4),
d) removing the UV cured image (2),
The time interval between jetting and curing the image is at least 50 ms, preferably at least 75 ms, most preferably at least 100 ms.

It has been found that nozzle clogging of ink jet printheads may be prevented when the time interval between jetting and curing is as described above.

In a preferred embodiment, the time interval between jetting and curing the image is less than 750 ms, more preferably less than 600 ms, most preferably less than 500 ms.

If the time interval between jetting and curing becomes too long, the image will be spread due to the spreading of the ink jet ink on the surface of the glass between the step of jetting the ink jet ink and the step of curing. It was recognized that the resolution of the may decrease.

In a preferred embodiment, the glass surface is cleaned prior to printing the UV curable ink jet ink. This is especially desirable when the glass surface is handled by hand and is not gloved. Cleaning removes dust particles and greases that can interfere with the adhesion of UV curable ink jet inks to the glass surface.

In a preferred embodiment of the method, the UV curing in step b) is carried out using UVLEDs.

In another preferred embodiment of the method, the UV-cured image is preferably before etching, preferably between UV-curing step b) and etching step c), preferably for 10 to 45 minutes. A heat treatment at 130 to 170° C., more preferably at 150° C. for 20 to 30 minutes is provided.

Suitable heating devices include devices that circulate hot air, ovens and infrared sources.

The heating device may be arranged, at least in part, in combination with a printhead of an ink jet printing machine that moves with it so as to apply the radiation immediately after ejection. In such a case, the ink jet printer is preferably equipped with some type of infrared source, for example infrared, such as an infrared laser diode or an infrared LED.

The preferred and effective infrared source has a maximum emission of between 0.8 and 1.5 μm. Such infrared sources are sometimes referred to as NIR sources or NIR dryers. In a preferred form, the NIR source is in the form of a NIR LED that can be easily mounted on the reciprocating system of multiple ink jet printheads in a multipass ink jet printing device.

NIR radiation energy is rapidly transmitted into the depth of the ink jet ink layer, removing water and solvents throughout the thickness of the layer, while conventional infrared energy and hot air energy are absorbed primarily at the surface, then It is gradually guided through the ink layer, which usually results in a slower removal of water and solvent.

In order to obtain a sufficiently thick and etch resistant UV cured image, the jetting step (a) and the UV curing step (b) are repeated 2, 3, 4 or 5 or more times before the etching step (c). There is a case. Alternatively, the jetting step (a) is repeated 2, 3, 4 or 5 or more times before the curing step (b) to obtain a sufficiently thick and etch resistant UV cured image.

Etching step (c) may also be repeated 2, 3 or 4 or more times to obtain sufficient etching depth.

According to another embodiment of the method, a UV curable ink jet ink containing a colorant is jetted onto at least a portion of the etched image. Adding color to at least a portion of the etched image may further enhance the decorative value of the image. Preferably, the white base layer is first applied to the areas where the color is to be printed.

The UV cured image is preferably removed from the glass surface by stripping or solubilizing in an alkaline stripping solution. Stripping typically results in flaking of the removed UV cured image in a stripping solution.

In a particularly preferred embodiment, the UV cured image is removed by solubilizing the UV cured image in an aqueous alkaline solution. Solubilizing the UV cured image may solve the above flake size problem.

The UV cured image is preferably solubilized within 15 minutes, more preferably within 10 minutes, and most preferably within 5 minutes.

Thus, the etched glassware (10) obtained by the method according to the invention corresponds to (i) the areas not previously covered by the UV-cured image (3), ie the "negative" of the UV-cured image. And (ii) a smooth area (6) corresponding to the area covered by the UV cured image (2).

The desired pattern or patterns on the glass product may be formed by the etched areas (4) or alternatively by the smooth areas (6).

The pattern may be a logo, characters (texts), drawings (drawings), or the like. The glass product produced by the method according to the invention may contain only one pattern or several, identical or different patterns distributed on the glass product.

Etched glass is usually due to its roughness and in particular the Rz (mean roughness depth) and Rsm (mean width of profile elements) parameters (expressed in μm) and the ratio Rz/Rsm between these two parameters. Is represented by. According to one embodiment, the etched area (4) of the glassware obtained by the method of the present invention has an Rz value of more than 9 μm and less than 22 μm and a Rz/Rsm ratio of more than 0.12 and less than 0.30. Figure 4 shows a defined, preferred surface roughness.

Depending on the roughness obtained, the selectively etched glass sheet may have different applications. For example, it may be used for decorative applications or, if the resulting roughness is high, for non-slip flooring, floor or stair applications.

Glass substrates
Glassware is made of glass, which may belong to various categories.

Thus, the glass is evenly distributed throughout its body, such as soda-lime-silica type glass, borate glass, lead glass, such as inorganic colorants, oxide compounds, viscosity modifiers and/or melt promoters. In some cases, the glass includes one or more of the additives listed above.

The glass is preferably of the soda-lime-silica type.

The glass may be transparent, ultra-transparent or tinted in its body.

Glass surface means not only the non-planar outer surface of the glass product, but also the flat outer surface.

The process according to the invention is preferably used for planar surfaces, especially glass sheets.

The glass sheet may be a perfectly smooth glass sheet or a glass sheet that has already been etched.

According to a preferred embodiment, the glass sheet is a sheet of float glass.

Very preferably, the glass sheet is a soda-lime-silica type float glass sheet.

The glass sheet may have any thickness. The thickness is preferably in the range 0.7 to 20 mm.

The process according to the invention is particularly suitable for selectively etching large areas of glass, for example glass sheets having a surface area of at least 5 m ² .

However, the method may also be used to selectively etch smaller surface areas, for example 0.5 m ² dimensional surface areas.

The glass sheet may be thermally, chemically, tempered, annealed or cured.

In order to comply with certain safety standards, the glass sheets may be laminated, that is to say they are wound together with other glass sheets by means of a thermoplastic film.

In the method according to the present invention, one or both surfaces of the glass sheet may be selectively etched to form a pattern on one or both surfaces of the glass sheet.

Suitably, the pattern is formed on one surface of the glass sheet. If the etching step is carried out by dipping the glass sheet in an etching solution, one surface of the glass sheet is completely covered with a protective layer for protecting the surface from the etching solution. Such a protective layer may be applied on the glass surface by any suitable application method, however, such a protective layer is also used for forming an image on the other side of the glass sheet. It is preferably applied by the step of jetting a curable ink jet ink and curing.

Etching step The etching solution used in the etching step of the method according to the invention is preferably an aqueous solution of hydrofluoric acid.

The etching solution typically has a pH between 0 and 5.

The acidic etching solution may further include, in addition to hydrofluoric acid itself, salts of this acid, other acids such as HCl, H ₂ SO ₄ , HNO ₃ , acetic acid, phosphoric acid and/or their salts (eg, Na ₂ SO ₄ , K ₂ SO ₄ , (NH ₄ ) ₂ SO ₄ , BaSO ₄ , etc.) and small proportions of optional auxiliaries (eg acid/base buffer compounds or compounds that promote the diffusion of solutions) ) May be included.

Alkali and ammonium salts such as sodium, potassium and ammonium hydrofluoride or bifluoride are preferred.

The time of the etching process, ie the time the glass plate is immersed in the etching solution, may vary as a function of the etching solution used and the amount of glass that has to be removed.

For productivity reasons, the etching step is preferably carried out within a time frame of less than 1 hour, preferably 5 to 45 minutes, more preferably 10 to 30 minutes.

Increasing the temperature generally accelerates the etching process. The etching step is preferably carried out at a temperature between 20 and 50° C., more preferably at room temperature.

The etching step may preferably be carried out by spraying under a pressure of at least 1 bar, more preferably 1 to 2 bar.

In a preferred embodiment, the etching step is carried out by immersing the glass sheet containing the UV cured image in an etching solution. For example, glass sheets may be transported at a particular rate in a dip bath containing an etching solution.

The etching process may be performed in one process or in two, three, four or more etching processes.

When multiple etching steps are used, all etching steps may have the same operating conditions (ie, the same etching solution, etching time and etching temperature), or the etching steps may have different operating conditions.

The UV curable ink jet printed image is suitably heat treated prior to the etching step, preferably at 130 to 170°C for 10 to 45 minutes, more preferably at 150°C for 20 to 30 minutes.

Following the etching step, it is preferably washed with water to remove any residual etchant.

Stripping Step After the etching step, the UV cured image is preferably removed in an alkaline stripping solution. Such alkaline stripping solutions are usually aqueous solutions having a pH>10.

The stripping solution or stripping bath preferably comprises an alkali metal hydroxide such as soda, potassium carbonate, sodium or potassium hydroxide, or such as mono- or tri-ethanolamine and tetramethylammonium hydroxide. It is an alkaline solution of an amine base. A suitable stripping solution contains at least 2% by weight sodium or potassium hydroxide. The stripping solution in use preferably has a temperature between 30°C and 85°C, more preferably between 40°C and 55°C. The stripping solution is preferably substantially free of organic solvent, and most preferably completely free of organic solvent.

In a preferred embodiment, spraying is used to apply the stripping solution.

Operating pressure by using a spray during the stripping process is believed to increase the stripping rate, and improves the flake degradation rate.

The equipment for performing the etching and stripping steps depends on the application and dimensions of the glass product.

Etching baths may be used through which glassware carrying one or more cured UV cured images is conveyed at a controlled rate. A simple bath for etching, in which a glass substrate is immersed in an etching solution for a specific time and heated at a specific temperature, is the simplest idea of a suitable apparatus.

UV curable ink jet inks UV curable ink jet inks are printed and UV cured on the glass surface to form a UV cured image that protects the glass surface from the etching solution.

The UV curable ink jet ink may be curable by cations, but it is preferably a free radical UV curable ink jet ink. UV curable ink jet inks may be cured by e-beam, but are preferably cured by UV light, more preferably UV light from a UVLED UVLED.

The viscosity of UV curable ink jet inks for reliable industrial ink jet printing is preferably 45 at 20 mPa.s. s or less, more preferably 1 to 18 mPa.s at 45°C. s, and most preferably 4 to 14 mPa.s at 45°C. between s.

For good image quality and adhesion, the interfacial tension of UV curable ink jet inks is preferably in the range of 18 mN/m to 70 mN/m at 25°C, more preferably about 20 mN/m to about 40 mN at 25°C. /M range.

In a preferred embodiment of the solubilizable UV curable ink method, the UV cured image is removed by solubilizing the UV cured image in an alkaline aqueous solution, which filters any flakes from the stripping solution. It means that there is nothing that is not necessary.

UV curable ink jet inks are preferably a) one or more photoinitiators, b) an optional colorant that decolorizes, preferably at a pH above 10, c) a polyfunctional monomer or oligomer. One or more hydrolyzable polyfunctional monomers or oligomers, in which at least one alkaline hydrolyzable group is arranged in the atom chain between the two polymerizable groups of , ethylene oxide or oligo - ethylene oxide groups, tertiary amine groups, 3 or more pK acidic and having _a, at least one functional selected from the group consisting of an aromatic or non-aromatic heterocyclic group 5- to 7-membered One or more water-absorption controlling monomers, which are monofunctional or difunctional monomers containing groups.

The hydrolyzable polyfunctional monomer or oligomer results in a cured ink jet image that is completely dissolved in the stripping solution, which causes degradation of the cured ink jet image in the stripping solution. ..

However, it is necessary to include a second monomer to obtain an acceptable manufacturing time. The water absorption modifier monomer is responsible for the swelling of the cured ink image in the stripping solution. This accelerates the dissolving of the cured ink image by the alkali contained in the stripping solution.

In a preferred embodiment, at least one alkaline hydrolyzable group located in the chain of atoms between the two polymerizable groups of the multifunctional monomer or oligomer is
Formulas H-1 to H-4:

[In the formula,
Q represents an atom necessary for forming a 5-membered aromatic ring group, Z represents an atom necessary for forming a 5- or 6-membered ring group, and a dotted line represents a residue of a polyfunctional monomer or oligomer. Represents a bond to
Is selected from the group consisting of.

In a further preferred embodiment, the at least one alkaline hydrolyzable group H-3 is selected from the group consisting of imidazole groups, benzimidazole groups, triazole groups and benzotriazole groups.

In a further preferred embodiment, the at least one alkaline hydrolyzable group H-4 is selected from the group consisting of succinimido and phthalimido groups.

In a particularly preferred embodiment, at least one alkaline hydrolyzable group is an oxalate ester group.

The one or more hydrolyzable polyfunctional monomers or oligomers are preferably acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, styrene groups, maleate groups, fumarate groups, itaconate groups, vinyl ether groups, vinyl ester groups. , An allyl ether group and an allyl ester group, and a polymerizable group independently selected from the group consisting of allyl ether group and allyl ester group.

Typical of hydrolyzable polyfunctional monomers and oligomers in which at least one alkaline hydrolyzable group is arranged in the atom chain between the two polymerizable groups of the polyfunctional monomer and the oligomer. Non-limiting examples are given in Table 1.

One or more hydrolyzable polyfunctional monomers or oligomers in which at least one alkaline hydrolyzable group is arranged in the atom chain between two polymerizable groups of the polyfunctional monomer or oligomer Is preferably contained in the UV curable ink jet ink in an amount of at least 25% by weight, more preferably at least 30% by weight, based on the total weight of the UV curable ink jet ink.

UV curable ink jet inks preferably contain one or more water absorption modifier monomers. Water adjusted monomers, hydroxyl group, ethylene oxide or oligo - ethylene oxide groups, tertiary amine, an acidic group having 3 or more pK _a, and is selected from 5 to the group consisting of 7-membered aromatic or non-aromatic heterocycle A monofunctional or difunctional monomer containing at least one functional group.

In a preferred embodiment, the one or more water absorption regulating monomers is at least selected from the group consisting of hydroxyl groups, ethylene oxide or oligo-ethylene oxide groups, carboxylic acid groups, phenolic groups, 5- to 7-membered lactam groups and morpholino groups. It contains one functional group.

In the most preferred embodiment, the one or more water absorption regulating monomers comprises at least one functional group selected from the group consisting of ethylene oxide or oligo-ethylene oxide groups, hydroxyl groups and morpholino groups.

The water absorption controlling monomer is preferably a monofunctional monomer.

The one or more water absorption controlling monomers preferably contain a polymerizable group selected from the group consisting of acrylate groups, methacrylate groups, acrylamide groups and methacrylamide groups.

The one or more water absorption control monomers preferably contain a polymerizable group selected from the group consisting of acrylate groups and acrylamide groups.

Suitable water absorption modifier monomers are provided in Table 2, but are not limited to them.

The one or more water absorption modifying monomers are preferably included in the UV curable ink jet ink in an amount of at least 20% by weight, based on the total weight of the UV curable ink jet ink.

Strippable UV curable ink jet inks UV cured images may be stripped from the surface of the glass into flakes by an aqueous alkaline solution after etching. This means that UV cured images are resistant to acidic etchants, but not alkaline stripping baths. Certain UV curable ink jet ink compositions may be used to achieve this.

The strippable UV curable ink jet ink preferably comprises a polymerizable composition, wherein at least 80%, preferably at least 90%, and most preferably 100% by weight of the polymerizable composition is
a) 15.0 to 70.0% by weight of acrylamide,
b) 20.0 to 75.0% by weight of polyfunctional acrylates, and c) 1.0 to 15.0% by weight of monofunctional (meth) containing carboxylic acid groups, phosphoric acid groups or phosphonic acid groups. Acrylate:
Where all weight percentages (wt %) are based on the total weight of the polymerizable composition.

The strippable UV curable ink jet ink has at least 15.0 to 70.0 wt%, preferably at least 20.0 to 65.0 wt%, and most preferably in the polymerizable composition. At least 30.0 to 60.0% by weight of acrylamide, where all weight percentages (% by weight) are based on the total weight of the polymerizable composition.

A single acrylamide or a mixture of acrylamides may be used.

Suitable acrylamides are disclosed in Table 3.

In a preferred embodiment of the UV curable ink jet ink, the acrylamide is cyclic acrylamide.

In the most preferred embodiment of the UV curable ink jet ink, the acrylamide is acryloylmorpholine.

The strippable UV curable ink jet ink is preferably at least 20.0 to 75.0% by weight, preferably 30.0 to 65.0% by weight and most preferably 40% by weight in the polymerizable composition. 0.0 to 55.0% by weight of polyfunctional acrylate, where all weight percentages are based on the total weight of the polymerizable composition.

A single multifunctional acrylate or a mixture of multifunctional acrylates may be used.

In a preferred embodiment, the polyfunctional acrylate is dipropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol (2x propoxylated) diacrylate, pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate. , Trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, tripropylene glycol diacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate and polyethylene glycol diacrylate.

In the most preferred embodiment of the UV curable ink jet ink, the polyfunctional acrylate comprises neopentyl glycol hydroxypivalate diacrylate.

The strippable UV curable ink jet ink comprises at least 1 to 15% by weight, preferably 2 to 12% by weight, and most preferably 4 to 8% by weight of carboxylic acid groups in the polymerizable composition. It includes (meth)acrylates containing phosphoric acid groups or phosphonic acid groups, where all weight percentages (wt %) are based on the total weight of the polymerizable composition.

Suitable examples of carboxylic acid group-containing monofunctional (meth)acrylates are of the formula (I):

[Wherein R represents a hydrogen atom or a methyl group, preferably a hydrogen atom, and Z represents a divalent organic group]
And a compound represented by.

Preferable examples of Z are *-(CH2)n-* [where n represents an integer of 2 to 12], *-CH2-CH2-O-CO-Z'-* [where Z'is Represents a divalent organic group], *-C6H4-*, *-C6H4-(CH2)n-* [where n represents an integer of 1 to 12], *-(CH2)n- C6H4-* [where n represents an integer from 1 to 12] and *-(CH2)n-O-C6H4-* [where n represents an integer from 1 to 12], and * is a binding site. Represents

Suitable examples of (meth)acrylates containing carboxylic acid groups are disclosed in Table 4.

Suitable examples of the (meth)acrylate containing a phosphoric acid group or a phosphonic acid group include 2-(methacryloyloxy)ethyl phosphate, hydroxyethyl methacrylate phosphate and bis-(2-methacryloyloxyethyl)phosphate.

Suitable examples of the (meth)acrylate containing a phosphoric acid group have the formula P-1 or P-2:

[Wherein R represents C _n H _2n+1 , where n represents an integer between 6 and 18].

Suitable examples of (meth)acrylates containing phosphate groups are disclosed in Table 5.

In a particularly preferred embodiment of the UV curable ink jet ink, the (meth)acrylate containing carboxylic acid groups, phosphoric acid groups or phosphonic acid groups is 2-carboxyethyl acrylate, 2-acryloylethyl succinate, and 2- It is selected from the group consisting of hydroxyethyl methacrylate phosphate.

Non-stripable UV curable ink jet inks Many UV curable ink jet inks that exhibit excellent adhesion to the glass surface are known in the art, but most of them are stripes. It cannot be ripped or solubilized.

The non-stripping UV curable ink jet ink suitably comprises a colorant, preferably a colored pigment. The UV cured image obtained with the UV curable ink jet ink containing the colorant becomes visible, allowing a quality check of the composition.

There is no practical limitation on the polymerizable composition as long as the ink jet ink is etch resistant relative to other polymerizable compound non-stripping UV curable ink jet inks.

The strippable UV curable ink jet ink may contain other polymerizable compounds than those mentioned above. They may be included in the UV curable ink jet ink in an amount of 0 to 20% by weight, more preferably up to 15% by weight, and most preferably up to 10% by weight, all here The weight percentage (% by weight) is based on the total weight of the polymerizable composition.

The solubilizable UV curable ink jet ink also comprises, in addition to one or more hydrolyzable multifunctional monomers and oligomers, one or more other monomers and oligomers and one or more water absorption controlling monomers. In some cases, UV curable ink jet inks preferably consist of one or more hydrolyzable polyfunctional monomers and oligomers and one or more water absorption modifier monomers.

The solubilizable UV curable ink jet ink is preferably 25 wt% or less, more preferably 15 wt% or less, and most preferably, based on the total weight of the UV curable ink jet ink. It may include one or more other monomers and oligomers contained in the UV curable ink jet ink in an amount of 0 to 10% by weight.

Other polymerizable compounds may be monomers, oligomers and/or prepolymers. These monomers, oligomers and/or prepolymers may have different degrees of functionality. Mixtures containing combinations of mono-, di-, tri- and higher functionality monomers, oligomers and/or prepolymers may be used. The viscosity of UV curable ink jet inks may be adjusted by changing the ratio between the monomers and oligomers.

Other particularly suitable monomers and oligomers are those mentioned in EP 0911814 [0106] to [0115].

The colorant UV curable ink jet may be a substantially colorless ink jet ink, but it is preferred that the UV curable ink jet ink comprises at least one colorant. The colorant allows the glassware manufacturer to unambiguously visualize the temporary mask, thereby allowing visual inspection of quality.

The colorant may be a pigment or dye, but is preferably a dye that is not bleached by the UV curing process during the ink jet printing process of UV curable ink jet inks. Dyes generally exhibit higher light fading than pigments, but do not pose a problem with jettability. However, the colorant is most preferably a dye that is not affected by the UV curing step in the ink jet printing process. Dyes, unlike pigments and dispersants, usually do not induce sludge in the etching and stripping solutions.

Anthraquinone dyes have been found to exhibit negligible photobleaching under the usual UV curing conditions used for UV curable ink jet printing.

The pigment may be black, white, cyan, magenta, yellow, red, orange, purple, blue, green, brown, mixtures thereof, and the like. Colored pigments are described in HERBST, Willy, et al. Industrial Organic Pigments, Products, Properties, Applications. 3rd edition. Wiley-VCH, 2004. It may be selected from those disclosed by ISBN 3527305769.

Suitable pigments are disclosed in paragraphs [0128] to [0138] of WO 2008/074548.

The pigment particles in the ink jet ink must be small enough to allow free flow of ink through the ink jet printing device, especially at the jet nozzle. Furthermore, for maximum tinting strength, it is desirable to use small particles and delay settling. Most preferably, the average pigment particle size is 150 nm or less. The average particle size of the pigment particles is preferably determined using a Brookhaven Instruments Particle Sizer BI 90plus based on the principle of kinetic light scattering.

In a particularly preferred embodiment, the colorant in the UV curable ink jet ink is an anthraquinone dye such as Macrolex ^™ Blue 3R (CASRN 325781-98-4) from LANXESS.

Other suitable dyes include crystal violet and copper phthalocyanine dyes.

In a preferred embodiment, the colorant of the ink jet ink is a dye that decolorizes at a pH above 10.

In a preferred embodiment, the colorant is dissolved in the radiation curable ink jet ink, ie it is a dye. Dyes allow much faster decolorization compared to pigments. They also do not induce dispersion stability problems in ink jet inks due to settling.

In a first preferred embodiment, the colorant is represented by the open form of a lactone-based leuco dye. In a further preferred embodiment, the leuco dye is a leuco dye according to formula (I) to (VIII):

[Wherein R 1 and R 2 are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted Or, selected from the group consisting of an unsubstituted aryl or heteroaryl group, n and m independently represent an integer of 0 to 3, and R3 and R4 independently represent a substituted or unsubstituted alkyl group or an alkoxy group. And R5 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aralkyl group. Selected from the group consisting of substituted aryl or heteroaryl groups, halogen, alkoxy groups, esters, amides, amines and carboxylic acids, and o represents an integer from 0 to 4],

[In the formula, R8 and R9 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group. And a substituted or unsubstituted aryl or heteroaryl group, R10 and R11 are independently selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group and a substituted or unsubstituted alkynyl group, and n is Represents an integer of 0 to 3, and m represents an integer of 0 to 5],

[Wherein R 12, R 13, R 16 and R 17 are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted Selected from the group consisting of an aralkyl group and a substituted or unsubstituted aryl or heteroaryl group, R14 and R15 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group. , A substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl or heteroaryl group],

[Wherein R20 to R23 are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted Or selected from the group consisting of unsubstituted aryl or heteroaryl groups, R18 and R19 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups and alkoxy groups],

[R24 and R25 are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted Selected from the group consisting of aryl or heteroaryl groups, R26 to R29 are independently hydrogen, a substituted or unsubstituted alkyl group and two of the groups R26 to R29 forming a substituted or unsubstituted aromatic ring. Selected from the group consisting of the group formed],

[Wherein, R30 to R33 are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted Or selected from the group consisting of unsubstituted aryl or heteroaryl groups],

[Wherein R34 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl or heteroaryl R35 is hydrogen, an alkoxy group, a dialkylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or Selected from the group consisting of unsubstituted aralkyl groups and substituted or unsubstituted aryl or heteroaryl groups].

Typical examples of lactone-based leuco dyes are given in Table 6, but are not limited thereto.

In a second preferred embodiment, the colorant is a triarylmethane dye, more preferably a triarylmethane dye according to formula (IX):

[Wherein R36 is hydrogen, dialkylamino group, diarylamino group, alkylarylamino group, alkoxy group, halogen, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted Selected from the group consisting of a substituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl or heteroaryl group, R37 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group , A substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl or heteroaryl group, and X represents a counterion that supplements the positive charge.
Is represented by

In a third preferred embodiment, the colorants are represented by cyanine dyes, merocyanine dyes and oxonol dyes. Cyanine dyes according to general formulas (X) to (XIII):

[Wherein X represents a group selected from hydrogen, nitrile, nitro, halogen and sulfone, EWG represents an electrophilic group, preferably an ester group, and R38, R39 and R41 are independently substituted or substituted. Represents an unsubstituted alkyl group, R40 and 42 are independently selected from the group consisting of a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group, and Y represents a counterion for compensating the positive charge]
Are particularly suitable.

Other suitable colorants are of formulas (XIII) and (XIV):

[Wherein R43, R44 and R45 are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group. And a substituted or unsubstituted aryl or heteroaryl group, R46 is hydrogen, an alkoxy group, a halogen, a carboxy group or an ester thereof, a sulfonic acid or a salt thereof, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl. Group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl or heteroaryl group, R47 is hydrogen, a substituted or unsubstituted alkyl group , A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl or heteroaryl group, an amino group, an amide group and a sulfonamide group R48 is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aralkyl group and a substituted or unsubstituted aryl or Selected from the group consisting of heteroaryl groups]
Is represented by

In a particularly preferred embodiment, the colorant comprises at least one substituent capable of compatibilizing the colorant or its decolorized form with the aqueous stripping solution. The substituent capable of compatibilizing the colorant or the decolorized form thereof is preferably a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, a sulfuric acid or a half ester of a salt thereof, It is selected from the group consisting of mono- or diesters of phosphoric acid or its salts, phenolic groups, ethylene oxide groups and hydroxyl groups, the carboxylic acid groups, hydroxyl groups and ethylene oxide groups being particularly preferred.

Typical colorants according to formulas (IX) to (XIV) are given in Table 7, but are not limited thereto.

The colorant is included in the UV curable ink jet ink in an amount sufficient to impair the visible color to the pattern of the cured ink. In a preferred embodiment, the colorant is included in an amount of 0.1 to 6.0% by weight. For dyes, amounts of less than 2% by weight, more preferably less than 1% by weight, based on the total weight of the UV curable ink jet ink, are usually sufficient.

Photoinitiator Systems UV curable ink jet inks preferably include at least one photoinitiator, but may include photoinitiator systems that include multiple photoinitiators and/or coinitiators.

The photoinitiator in the UV curable ink jet ink is preferably a free radical initiator, more specifically a Norrish type I initiator or a Norrish type II initiator. Free radical photoinitiators are compounds that, upon exposure to actinic radiation, initiate the polymerization of monomers and oligomers by the formation of free radicals. Norrish type I initiators are initiators that are cleaved after excitation and immediately generate an initiating radical. Norrish type II initiators are photoinitiators that are activated by actinic radiation and form free radicals by abstraction of hydrogen from a second compound that becomes the actual initiating free radical. This second compound is called a polymerization synergist or coinitiator. In the present invention, both Type I and Type II photoinitiators may be used alone or in combination.

Suitable photoinitiators are BRADLEY, G.; , London, UK: John Wiley and Sons Ltd, 1998. p. 287-294, edited by CRIVELLO, J. V. , Et al. Photoinitiators
for Free Radical Cationic and Anionic Photopolymerization. It is disclosed in the second edition.

Specific examples of photoinitiators include the following compounds: benzophenone and substituted benzophenones, 1-hydroxycyclohexyl phenyl ketone, thioxanthones such as isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, benzyl-dimethyl ketal, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4 ,6-Trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethoxybenzoyldiphenylphosphine oxide, 2-methyl-1-[4-methylthio]phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy It may include, but is not limited to, -1,2-diphenylethan-1-one or 5,7-diiodo-3-butoxy-6-fluorone, or a combination thereof.

Commercially available photoinitiators appropriate, CIBA SPECIALTY commercial Irgacure ^TM 184 from ^{CHEMICALS, Irgacure TM 500, Irgacure TM} 369, Irgacure TM 1700, Irgacure TM 651, Irgacure TM 819, Irgacure TM 1000, Irgacure TM 1300, Irgacure TM 1870 , Darocur ^™
1173, Darocur ^™ 2959, Darocur ^™ 4265 and Darocur ^™ ITX, Lucerin ^™ TPO commercially available from BASF AG.
, Esacure ^™ KT046, Esacure ^™ available from LAMBERTI, Inc.
KIP150, Esacure ^™ KT37 and Esacure ^™ EDB,
SPECTRA GROUP LTD. Commercially available from H-Nu ^™ 470 and H-Nu ^™ 470X.

The photoinitiator may be a so-called diffusion hindered photoinitiator. Diffusion-inhibiting photoinitiators are photoinitiators that exhibit much lower mobility in the cured ink layer than monofunctional photoinitiators such as benzophenone. Several methods may be used to reduce the mobility of the photoinitiator. One method is to increase the molecular weight of the photoinitiator such that the diffusion rate is reduced, eg a polymeric photoinitiator. Other methods are to increase its reactivity so as to incorporate it into the polymeric network, eg polyfunctional photoinitiators (having 2, 3 or 4 or more photoinitiating groups) and polymerizable photoinitiators. ..

The diffusion-hindered photoinitiator for UV curable ink jet inks is preferably selected from the group consisting of non-polymeric polyfunctional photoinitiators, oligomeric or polymeric photoinitiators and polymerizable photoinitiators. To be done. Most preferably, the diffusion-inhibiting photoinitiator is a polymerizable or polymeric photoinitiator.

Suitable diffusion-inhibiting photoinitiators are benzoin ethers, benzyl ketals, α,α-dialkoxyacetophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, acylphosphine sulfides, α-haloketones, α-halosulfones. And one or more photoinitiating functional groups derived from a Norrish type I-photoinitiator selected from the group consisting of and phenylglyoxalate.

Suitable diffusion-inhibiting photoinitiators contain one or more photoinitiating functional groups derived from Norrish type II-initiators selected from the group consisting of benzophenones, thioxanthones, 1,2-diketones and anthraquinones.

Suitable diffusion-inhibiting photoinitiators are also described in EP 2065362 for difunctional and polyfunctional photoinitiators in paragraphs [0074] and [0080] and for polymeric photoinitiators. [0077] to [0080], and polymerizable photoinitiators are those disclosed in paragraphs [0081] to [0083].

The preferred amount of photoinitiator is preferably 0 to 50% by weight, more preferably 0.1 to 20% by weight, and most preferably of the total weight of the UV curable ink jet ink containing one initiator. It is preferably 0.3 to 15% by weight.

To further enhance photosensitivity, UV curable ink jet inks may further include coinitiators. Suitable examples of coinitiators are group 3: (1) tertiary aliphatic amines [eg methyldiethanolamine, dimethylethanolamine, triethanolamine, triethylamine and N-methylmorpholine], (2) aromatic amines [eg , Amylparadimethylaminobenzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate), 2-(dimethylamino)-ethylbenzoate, ethyl-4-(dimethylamino)benzoate and 2-ethylhexyl-4-( Dimethylamino)benzoate] and (3) (meth)acrylated amine [eg dialkylaminoalkyl(meth)acrylate, (eg diethylaminoethyl acrylate), or N-morpholinoalkyl(meth)acrylate (eg N-morpholinoethyl) -Acrylate)],. The preferred coinitiator is aminobenzoate.

When one or more coinitiators are included in the UV curable ink jet ink, these coinitiators are preferably diffusion-inhibited for safety reasons.

The diffusion-inhibiting coinitiator is preferably selected from the group consisting of non-polymeric difunctional or polyfunctional coinitiators, oligomeric or polymeric coinitiators and polymerizable coinitiators. More preferably, the diffusion-inhibiting coinitiator is selected from the group consisting of polymeric coinitiators and polymerizable coinitiators. Most preferably the diffusion inhibiting co-initiator is a polymerizable co-initiator having at least one (meth)acrylate group, more preferably at least one acrylate group.

UV curable ink jet inks preferably contain a polymerizable or polymeric tertiary amine co-initiator.

Suitable diffusion-inhibiting coinitiators are the polymerizable coinitiators disclosed in paragraphs [0088] to [0097] of EP2053101.

The UV curable ink jet ink is preferably in an amount of 0.1 to 50% by weight, more preferably 0.5 to 25% by weight, most preferably of the total weight of the UV curable ink jet ink. It contains (inhibition of diffusion) coinitiators in an amount of 1 to 15% by weight.

Polymerization Inhibitor The UV curable ink jet ink may contain a polymerization inhibitor. Suitable polymerization inhibitors include phenol-type antioxidants, hindered amine light stabilizers, phosphorus-type antioxidants, hydroquinone monomethyl ether commonly used in (meth)acrylate monomers, and hydroquinone, t-butyl. Catechol, pyrogallol may also be used.

Suitable commercially available inhibitors are, for example, Sumitomo Chemical Co. Ltd. Sumilizer ^™ GA-80, Sumilizer ^™ GM and Sumilizer ^™ GS, Genora from Rahn AG manufactured by
d ^TM 16, Genorad ^TM 18 and Genorad ^TM 20, Ciba.
Specialty Chemicals Irgastab from ^TM UV10 and Irgastab ^TM UV22, Tinuvin ^TM 460 and CGS20, Floorstab ^TM UV series from Kromachem Ltd (UV-1, UV -2, UV-5 and UV-8), Additol from Cytec Surface Specialties ^{It is a TMS} sequence (S100, S110, S120 and S130).

Since the excessive addition of these polymerization inhibitors is considered to reduce the sensitivity to curing, it is preferable to determine the amount capable of preventing polymerization before mixing. The amount of polymerization inhibitor is preferably less than 2% by weight of the total weight of the UV curable ink jet ink.

Polymer Dispersant When the UV curable ink jet ink comprises a colored pigment, the UV curable ink jet ink preferably comprises a dispersant for dispersing the pigment, more preferably a polymer dispersant.

Suitable polymeric dispersants are copolymers of two monomers, but they may contain 3, 4, 5 or 6 or more monomers. The properties of polymeric dispersants depend on both the nature of the monomers and their distribution in the polymer. The copolymer dispersant is preferably of the following polymer composition:
Statistically polymerized monomers (eg, monomers A and B polymerized to ABBAABAB); alternating polymerized monomers (eg, monomers A and B polymerized to ABABABAB); gradient polymerized monomers (eg, AAABAABBABBB) Polymerized monomers A and B);
Block copolymers (eg, monomers A and B polymerized to AAAAABBBBBB) where the length of each block (2, 3, 4, 5 or 6 or more) is important to the dispersability of the polymeric dispersant;
Graft copolymers (graft copolymers consisting of a polymer backbone with polymer side chains attached to the backbone); and mixed forms of these polymers, for example block-shaped gradient copolymers,
Have.

Suitable polymeric dispersants are listed in EP-A-A 1911814 under the section "Dispersants", more specifically in [0064] to [0070] and [0074] to [0077]. ing.

Commercial examples of polymeric dispersants are:
A DISPERBYK ^™ dispersant commercially available from BYK CHEMIE GMBH;
A SOLSPERSE ^™ dispersant commercially available from NOVEON;
TEGO ^™ DISPERS ^™ dispersants from EVONIK;
EDAPLAN ^™ dispersant from MUNZING CHEMIE;
ETHACRYL ^™ dispersant from LYONDELL;
GANEX ^™ dispersant from ISP;
• DISPEX ^™ and EFKA ^™ dispersants from CIBA SPECIALTY CHEMICALS INC;
• DISPONER ^™ dispersant from DEUCHEM; and • JOHNSON POLYMER. JONCRYL ^™ dispersant from
Is.

Surfactants UV curable ink jet inks may include at least one surfactant, but preferably do not include any surfactant. When no surfactant is included, the UV curable ink jet ink does not spread well on the glass surface, thereby allowing the formation of thin lines.

Surfactants can be anionic, cationic, nonionic or zwitterionic and are usually added in a total amount of less than 1% by weight based on the total weight of the UV curable ink jet ink.

Suitable surfactants include fluorinated surfactants, fatty acid salts, ester salts of higher alcohols, alkylbenzene sulfonate salts, sulfosuccinate ester salts of higher alcohols and phosphate ester salts (eg sodium dodecylbenzene sulfonate and sodium dioctyl sulfonate). Succinate), ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of fatty acid esters of polyhydric alcohols, and acetylene glycol and its ethylene oxide adducts (eg, polyoxyethylene nonylphenyl ethers, and AIR PRODUCTS). &
CHEMICALS INC. SURFYNOL ^™ 104, 104H, 440, 465 and TG) commercially available from

Suitable surfactants are selected from fluorosurfactants (such as fluorinated hydrocarbons) and silicone surfactants. The silicone surfactant is preferably a siloxane, and may be alkoxylated, polyether modified, polyether modified hydroxy functionalized, amine modified, epoxy modified, and other modifications or combinations thereof. May be Suitable siloxanes are polymers such as polydimethylsiloxane.

Suitable commercial silicone-based surfactants include BYK ^™ 333 and BYK ^™ UV3510 f from BYK Chemie.

In a preferred embodiment, the surfactant is a polymerizable compound.

Suitable polymerizable silicone-based surfactants are (meth)acrylated silicone-based surfactants. (Meth)acrylated silicone surfactants are most preferably acrylated silicone surfactants because acrylates are more reactive than methacrylates.

In a preferred embodiment, the (meth)acrylated silicone surfactant is a polyether modified (meth)acrylated polydimethylsiloxane or a polyester modified (meth)acrylated polydimethylsiloxane.

Surfactants are preferably included in the UV curable ink jet ink in an amount of 0 to 3% by weight, based on the total weight of the UV curable ink jet ink.

Preparation of ink jet inks The preparation of pigmented UV curable ink jet inks is well known to those skilled in the art. Suitable methods of preparation are disclosed in WO 2011/069943, paragraphs [0076] to [0085].

INKJET PRINTING DEVICE UV curable ink jet ink ejects droplets in a controlled manner through nozzles onto a moving substrate relative to one or more printheads.
It may be fired by more than one printhead.

A suitable printhead for ink jet printing systems is a piezoelectric head.

Piezo ink jet printing is based on the movement of a piezoceramic transducer when it is energized. Application of a voltage changes the shape of the piezoceramic transducer in the printhead to form a void, which is then filled with ink. When the voltage is turned off again, the ceramic expands to its original shape, which ejects a drop of ink from the printhead. However, the ink jet printing method according to the present invention is not limited to piezoelectric ink jet printing. Other ink jet printheads may be used, including various types such as continuous type.

Ink jet printheads typically scan laterally back and forth over the surface of a moving ink receiver. Inkjet printheads often do not print on the return trip. Bi-directional printing is preferred for high area throughput. Another suitable printing method may be carried out by using a full width page ink jet printhead or multiple staggered ink jet printheads that cover the entire width of the glass sheet. The one-pass printing method”. In the single pass printing method, the ink jet printhead typically remains stationary and the glass sheet is conveyed beneath the ink jet printhead.

For glass products having a three-dimensional shape that is not essentially two-dimensional, such as a glass sheet, ie, a sphere or a more complex object such as a combination of a cylinder with a cube, the printhead. May be fixed on a robot arm that can follow the shape of a three-dimensional object for applying UV curable ink jet inks. Such techniques are known in the art, for example in U.S. Pat. No. 20150427716, WO 2014/001850 and U.S. Pat. No. 2015009254.

Suitable ink jet printers that may be used in the method according to the invention are eg Agfa.
An Anapurna M series printing machine commercially available from Graphics.

Curing Devices UV curable ink jet inks may be cured by exposure to actinic radiation, such as electron beam or ultraviolet light, and preferably the image of the UV curable ink jet ink is ultraviolet light. Is more preferably cured using UVLED UVLED curing.

In ink jet printing, the curing means may be arranged in combination with a printhead of an ink jet printing machine moving with it so that the curing liquid is exposed to the curing line immediately after jetting.

UVLEDs In such an arrangement, with the exception of UVLEDs, it can be difficult to provide a sufficiently small radiation source connected to and moving with the printhead. Therefore, use a statically fixed source, eg a cured UV-ray source connected to the radiation source by flexible radiation conducting means, such as a bundle of optical fibers or a flexible tube with internal reflection. There is a case.

Alternatively, the actinic radiation may be supplied to the radiation head from a fixed source by a mirror arrangement, which includes a mirror above the radiation head.

The radiation source may also be an elongated source that extends across the substrate to be cured. It may be adjacent to the transverse path of the printhead such that subsequent rows of images formed by the printhead pass below the radiation source in a stepwise or continuous manner.

High or low pressure mercury lamps, cold cathode tubes, UV light, UV LEDs, UV lasers and flashlamps, as long as some of the emitted light can be absorbed by the photoinitiator or photoinitiating system. (Flash
Any source of UV radiation, such as light) may be used as the radiation source. Of these, the preferred sources are those exhibiting a relatively long wavelength UV-contribution with a dominant wavelength of 300 to 400 nm. Specifically, UV-A light sources are preferred due to the reduced scattering of light rays which results in more efficient internal curing.

UV light is generally
UV-A: 400 nm to 320 nm,
UV-B: 320 nm to 290 nm,
UV-C: 290 nm to 100 nm,
Are classified as UV-A, UV-B and UV-C.

In a preferred embodiment, the UV curable ink jet ink is cured by UVLED UVLED. The ink jet printing device preferably comprises one or more UVLED UVLEDs with a wavelength longer than 360 nm, preferably one or more UVLED UVLEDs with a wavelength longer than 380 nm, and most preferably a UVLED UVLED with a wavelength of about 395 nm. ..

Further, it is possible to use two light sources of different wavelengths or illuminance, either sequentially or simultaneously to cure the ink image. For example, the first UV source may be selected to be UV-C rich, especially in the range of 260 nm to 200 nm. The second UV-source may then be a UV-A-rich lamp, for example a gallium-doped lamp, or a different lamp rich in both UV-A and UV-B. The use of two UV-sources has been found to have advantages such as rapid cure speed and high degree of cure.

To accelerate curing, ink jet printing devices often include one or more oxygen depletion units. The oxygen depletion unit is a blanket of nitrogen or other relatively inert gas (eg, CO ₂ ), with adjustable location and adjustable inert gas concentration to reduce the oxygen concentration in the curing environment. To place. Residual oxygen levels are usually kept low down to 200 ppm, but are generally in the range of 200 ppm to 1200 ppm.

Materials All materials used in the following examples are from ALDRICH CHEMICAL Co. unless otherwise stated. It was readily available from standard manufacturers such as (Belgium) and ACROS (Belgium). The water used was deionized water.

ACMO is an acroylmorpholine commercially available from RAHN.

INHIB has the composition:

Is a mixture forming a polymerization inhibitor having

Cupferron ^™ AL is WAKO CHEMICALS LTD. Aluminum N-nitrosophenylhydroxylamine from

Dye-1 is a blue anthraquinone dye commercially available from LANXESS as Macrolex ^™ Blue 3R.

ITX is a mixture of isomers of 2- and 4-isopropylthioxanthone commercially available from BASF as Darocur ^™ .

EPD is ethyl 4-dimethylaminobenzoate commercially available from RAHN as Genocure ^™ EPD.

TPO is a photoinitiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, commercially available from BASF as Darocur ^™ TPO.

BAPO is phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide commercially available from BASF.

IC907 is the photoinitiator 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one commercially available as Irgacure ^™ 907 from BASF.

Macrolex ^™ Blue 3R is a blue anthraquinone dye from LANXESS.

DPGDA is dipropylene glycol diacrylate commercially available from SARTOMER as Sartomer ^™ SR508.

2-HEA is 2-hydroxyethyl acrylate from ALDRICH.

MADAME is N,N-dimethyl 2-aminoethyl methacrylate commercially available from ARKEMA France as Norsocryl ^™ MADAME.

EOEOEA is an ethoxyethoxyethyl acrylate commercially available from SARTOMER as Sartomer ^™ SR256.

VEEA or 2-(2-vinyloxy-ethoxy)-ethyl acrylate is available from Nippon Shokubai. Supplied by

IDA is an isodecyl acrylate commercially available from SARTOMER as Sartomer ^™ SR395.

SR606A is a neopentyl glycol hydroxyl pivalate diacrylate commercially available from SARTOMER as Sartomer ^™ SR606A.

HDDA is a 1,6-hexanediol diacrylate commercially available from SARTOMER as Sartomer ^™ SR238.

TMPTA is trimethylolpropane trimethacrylate commercially available from SARTOMER as Sartomer ^™ SR350.

NPGDA is a neopentyl glycol (2x propoxylated) diacrylate commercially available from SARTOMER as Sartomer ^™ SR9003 f.

PETA is a pentaerythritol tetraacrylate commercially available from Sartomer as Sartomer 295.

CEA is 2-carboxyethyl acrylate from ALDRICH.

SR9054 is a 2-hydroxyethylmethacrylate phosphate commercially available from SARTOMER as Sartomer ^™ SR9054.

CN146 is a 2-acryloxyethyl hydrogen phthalate commercially available from SARTOMER as Sartomer ^™ CN146.

IC819 is a photoinitiator bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide commercially available as Irgacure ^™ 819 from BASF.

PEG200DA has n=4, a polyethylene glycol (MW200) diacrylate commercially available from SARTOMER as Sartomer ^™ SR259:

Is.

HDDA is commercially available from SARTOMER as Sartomer ^™ SR238
6-hexanediol diacrylate:

Is.

HYDRO-8 is an oxalate monomer similar to PEG200DA:

Is.

The synthesis of oxalic acid bis-[2-(2-acryloyloxy-ethoxy)-ethyl]ester (HYDRO-8) was carried out as follows:

First step: Synthesis of 2-(2-hydroxy-ethoxy)-ethyl acrylate 55.9 g (0.3 mol) of 2-(2-vinyloxy-ethoxy)-ethyl acrylate was dissolved in 100 ml of acetone. 27 g (1.5 mol) of water and 0.6 g (6 mmol) of methanesulphonic acid were added. The reaction was continued at room temperature for 4 hours. The reaction mixture was diluted with 500 ml methylene chloride and extracted with 250 ml water. The organic fraction was dried over MgSO _4, and evaporated under reduced pressure. 2-(2-Hydroxy-ethoxy)-ethyl acrylate was subjected to TLC-chromatography (Partisil KC18F supplied by Whatman, eluent: methanol/0.5N NaCl 80/20, R _f : 0.83, trace only. (2-Vinyloxy-ethoxy)-ethyl acrylate, _Rf : 0.66
And a compound according to the following structural formula, R _f : 0.9).

2-(2-hydroxy-ethoxy)-ethyl acrylate was used without further purification.

Second step: Synthesis of oxalic acid bis-[2-(2-acryloyloxy-ethoxy)-ethyl] ester 30.4 g (0.19 mol) of 2-(2-hydroxy-ethoxy)-ethyl acrylate, 19.8 g (0.196 mol) triethylamine and 1.3 g (5.7 mmol) BHT were dissolved in 140 ml methylene chloride. The solution was cooled to -10°C. A solution of 12.1 g (0.095 mol) of oxalyl chloride in 70 ml of methylene chloride was added dropwise while maintaining the temperature at -10°C. The reaction was allowed to continue at 0° C. for 1 hour and then for 16 hours at room temperature. The reaction mixture was added to 200 g ice and the mixture was extracted with 200 ml methylene chloride. The organic fraction was extracted with 200 ml 1N hydrochloric acid solution, 200 ml saturated NaHCO ₃ solution and 200 ml saline. The organic fraction was dried over MgSO _4, and evaporated under reduced pressure. The crude product
Purified using preparative column chromatography using a Prochrom LC80 column packed with 10 μm and methylene chloride/ethyl acetate 90/10 as eluent. 19.1 g of oxalic acid bis-[2-(2-acryloyloxy-ethoxy)-ethyl] ester was isolated (y: 54%). The compound was purified using TLC-chromatography (TLC silica gel 60F ₂₅₄ , supplied by Merck, eluent: methylene chloride/ethyl acetate, 83/17, R _f : 0.42) and LC-MS as described below. Analysis was carried out according to the method (residence time: 6.6 minutes, precision 96.2 area %).

HYDRO-11 is an oxalate monomer similar to HDDA:

Is.

The synthesis of oxalic acid bis-(4-acryloyloxy-butyl) ester (HYDRO-11) was carried out as follows.

51.3 g (0.3 mol) 4-hydroxy-butyl acrylate, 31.4 g (0.31 mol) triethylamine and 2 g (9 mmol) BHT were dissolved in 200 ml methylene chloride. The reaction mixture was cooled to -10°C. A solution of 19.0 g (0.15 mol) oxalyl chloride in 100 ml methylene chloride was added dropwise maintaining the temperature at -10°C. The reaction was continued at 0° C. for 1 hour and then at room temperature for 16 hours. The reaction mixture was poured into 500 g of ice and the mixture was stirred for 1 hour. The mixture was extracted twice with 200 ml methylene chloride. The pooled organic fraction was extracted with 300 ml of 1N hydrochloric acid solution, 300 ml of saturated NaHCO ₃ solution and twice with 200 ml of saline. The organic fraction was dried over MgSO _4, and evaporated under reduced pressure. The crude product
Purified using preparative column chromatography using a Prochrom LC80 column packed with 10 μm and methylene chloride/ethyl acetate 90/10 as eluent. 22 g of oxalic acid bis-(4-acryloyloxy-butyl)-ester was isolated (y: 43%). The compound was subjected to TLC-chromatography (TLC silica gel 60 F ₂₅₄ supplied by Merck, eluent: methylene chloride/ethyl acetate, 96/4, R _f : 0.3), GC (residence time: 12.2 min, Accuracy: 99.6 area%) and GC-MS, both were analyzed according to the following method.

NVL is n-vinylcaprolactam commercially available from BASF.

PEA is a phenoxy acrylate commercially available from SARTOMER as Sartomer ^™ SR339C.

Measurement method 1. Etching resistance (ER)
The etching resistance was evaluated by controlling if the ink layer was still present after etching and rinsing. The evaluation was performed according to the criteria shown in Table 9.

2. Strippability (SB) and flakes The strippability (SB) was treated by stirring to give a dried sample that was etched in a beaker containing 2% NaOH-solution at 50°C. Decided to use.

The peeling time of the UV curable ink jet printing layer from the glass surface, that is, the peeling time was measured. The evaluation was performed according to the criteria described in Table 10.

Flake formation was observed after the peeling of the UV curable ink jet print layer started.

3. Viscosity The viscosity of the formulations was measured at 45° C. using a “Robotic Viscometer Type (robot viscometer type) VISCObot” from CAMBRIDGE APPLIED SYSTEMS.

4. Curing Rate After printing on a glass sheet and curing, the ink jet layer was evaluated by finger feel. The evaluation was performed according to the criteria described in Table 11.

This example illustrates the effect of the time interval between jetting and curing an image on a glass sheet on printhead clogging.

The glass plate was cleaned with a cotton pad soaked in isopropanol to remove dust and grease particles from the glass surface.

After drying, the image was printed on a glass plate using an MJK 2013 ink jet printer equipped with a Konica Minolta 1024 print head with a drop volume of 6 pL in 8 passes (1440 x 1440 dpi) and an ink jet having the composition of Table 12. It was printed with ink to form a 16 μm thick image. It was then cured an image by SubZero LED090 from Integration Technology (395nm-7W / cm 2).

The time interval between jetting and curing (Δtime) was varied by adjusting the print speed as shown in Table 13.

The clogging was evaluated after printing for 3 days. Partial clogging of the print nozzles of the printhead resulted in poor drop placement accuracy, while complete clogging resulted in "missing" drops on the glass surface. The results are shown in Table 13.

From the results in Table 13, it is clear that a time interval between jetting and curing of at least 50 ms results in improved printing performance.

This example represents the manufacture of etched glassware using UV curable ink jet printing.

The glass plate was cleaned with a cotton pad soaked in isopropanol to remove dust and grease particles from the glass surface.

After drying, the images were printed on a glass plate using a MJK2013 ink jet printer equipped with a Konica Minolta 1024 printhead with a drop volume of 6 pL in 8 passes (1440 x 1440 dpi) and the composition of Table 12 (Example 1). Printing with an ink jet ink having a thickness of 16 μm. Then the image was cured by SubZero LED090 from Integration Technology (395nm-7W / cm 2).

The time interval between injection and cure was 360 ms.

The cured image was subjected to an additional heat treatment at 150° C. for 30 minutes.

Next, the glass plate was immersed in an etching solution having the composition shown in Table 14 for 1 to 2 minutes at room temperature.

The glass substrate was then rinsed with clean water and dried.

The obtained etching depth was 0.06 to 0.1 mm.

The etched glass plate was then exposed to an alkaline stripping bath (containing 7% ethanolamine) at 50°C for 2 minutes, then rinsed with water for 90 seconds and dried.

A matte image was formed in the glass, leaving a decorative pattern. An example of such an image is shown in FIG.

This example represents printing a UV curable ink jet ink in which the UV cured image is stripped and solubilized after etching. This eliminates the need to filter out flakes of the cured ink image.

Preparation of UV curable ink jet inks UV curable ink jet inks C-1 to C-3 and 1-1 to 1-3 were prepared according to Table 15. Weight percentages (wt %) were based on the total weight of the UV curable ink jet ink. UV curable ink jet ink C-1 does not contain hydrolyzable polyfunctional monomers or oligomers, while UV curable ink jet ink C-2 does not contain water absorption controlling monomers. C-3 is the UV curable ink disclosed in WO 2013/189762.

Evaluation and Results The glass plate was cleaned with a cotton pad soaked in isopropanol to remove dust and oil particles.

After drying, the image was printed on a glass plate using an Anapurna Mw ink jet printer (available from Agfa Graphics NV) equipped with a Konica Minolta 512M printhead with a drop volume of 14 pL in 8 passes (1440 x 1440 dpi). , UV curable ink jet inks C-1 to C-3 and 1-1 to 1-3. The image was then cured with a Hg lamp. The time interval between jetting and curing was between 180 and 500 ms.

The cured image was subjected to an additional heat treatment at 150° C. for 30 minutes.

The glass plate was then immersed in the etching solution whose composition is shown in Table 16 for 5 minutes at room temperature.

The glass plate was rinsed with water and dried.

Next, the etching resistance was evaluated as shown in Table 17.

The etched glass plate was exposed to an alkaline stripping bath (containing 2% NaOH) at 50° C. for 5 minutes, then rinsed with water for 90 seconds, dried, and stripped of the stripped and stripped ink layer. The shape was evaluated. The results are shown in Table 17.

From Table 17, the UV curable ink jet inks 1-1 to 1-3 were UV-curable, with the exception that the pattern of the cured ink in the alkaline stripping bath was completely dissolved in the blue liquid within 5 minutes. It must be clear that it gave results for etch resistance and strippability comparable to those of the curable ink jet inks C-1 to C-3.

By replacing the colorant Dye-1 with crystal violet, it was observed that the colored cured ink image in the alkaline stripping bath was completely dissolved in the colorless liquid within 5 minutes. By using crystal violet as a dye that decolorizes at pH above 10, two favorable effects were obtained. First, the cured ink image could be visually inspected prior to etching. Second, after multiple stripping steps, when the stripping solution begins to color, this forms an indicator to replace the stripping solution.

Preparation of UV curable ink jet inks UV curable ink jet inks C-4 to C-14 and UV curable ink jet inks 1-4 to 1-19 were prepared according to the composition of type A or B in Table 18. .. All weight percentages (wt %) were based on the total weight of the UV curable ink jet ink.

The amounts and types of monomers used in the ink jet polymerizable composition are shown in Table 19. All weight percentages (wt %) in Table 19 were based on the total weight of the polymerizable composition. Viscosity was measured and is shown in Table 21.

Evaluation and results The glass plate was cleaned with a cotton pad soaked in isopropanol to remove dust and oil particles.

After drying, the images were UV curable using an Anapurna Mw ink jet printer (commercially available from Agfa Graphics NV) equipped with a Konica Minolta 512M printhead with a drop volume of 14 pL in 8 passes (720 x 1440 dpi). The ink jet inks C-04 to C-14 and l-04 to -19 were printed on a glass plate. The image was then cured with a Hg lamp. The time interval between the injection step and the curing step was between 180 and 500 ms.

The cured image was subjected to an additional heat treatment at 150° C. for 30 minutes.

Next, the glass plate was immersed in the etching solution whose composition is shown in Table 20 for 5 minutes at room temperature.

The etched glass plate is exposed to an alkaline stripping bath (containing 2% NaOH) for 5 minutes at 50° C., then rinsed with water for 90 seconds, dried, and stripped and stripped ink layer. The shape was evaluated. The results are shown in Table 21.

From Table 21 it should be clear that only UV curable ink jet inks l-04 to l-19 gave excellent results. UV curable ink jet inks by replacing the acrylamide ACMO with other monomers that are also hydrophilic but (meth)acrylates, or by ignoring the range for acrylamide, polyfunctional acrylates and acidic monomers, Did not meet one or more requirements for conductor pattern fabrication.

Claims (7)

A method of making an etched glass product (10), comprising:
a) spraying the image (2) with UV curable ink jet ink on the surface of the glass product,
b) UV curing the image (2) using a UV LED,
c) heating the UV cured image,
d) etching the surface (3) not covered by the UV cured image to obtain an etched image (4),
e) including the step of removing the UV cured image (2),
The time interval between the step of ejecting the image and the step of curing is between 50 ms and 750 ms ,
Wherein a UV curable ink jet ink containing a colorant is jetted over at least a portion of the etched image,
Method. The method of claim 1, wherein the UV cured image is solubilized within 5 minutes. The UV curable ink jet ink is
a) one or more photoinitiators,
b) one or more hydrolyzable polyfunctional groups in which at least one alkaline hydrolyzable group is arranged in the atom chain between the two polymerizable groups of the polyfunctional monomer or oligomer. Monomer or oligomer,
c) hydroxyl groups, ethylene oxide or oligo - ethylene oxide groups of at least a tertiary amine group is selected from the group consisting of acidic and, 5 to 7-membered aromatic or non-aromatic heterocyclic group having 3 or more pK _a The method of claim 1, comprising one or more water absorption regulating monomers, which are monofunctional or difunctional monomers containing one functional group. 4. The method of claim 3 , wherein the one or more water absorption modifier monomers comprises at least one functional group selected from the group consisting of ethylene oxide or oligo-ethylene oxide groups, hydroxyl groups and morpholino groups. The at least one alkaline hydrolyzable group located in the atom chain between the two polymerizable groups of the polyfunctional monomer or oligomer has the formulas H-1 to H-4:
[In the formula,
Q represents an atom necessary for forming a 5-membered aromatic ring group, Z represents an atom necessary for forming a 5- or 6-membered ring group, and a dotted line represents a residue of a polyfunctional monomer or oligomer. Represents the bonds to (rest)]
The method of claim 3 , wherein the method is selected from the group consisting of: The at least one alkaline hydrolyzable group, arranged in the chain of atoms between the two polymerizable groups of the polyfunctional monomer or oligomer, has the formulas H-1 to H-4:
[In the formula,
Q represents an atom necessary for forming a 5-membered aromatic ring group, Z represents an atom necessary for forming a 5- or 6-membered ring group, and a dotted line represents a residue of a polyfunctional monomer or oligomer. Represents a bond to
The method of claim 4 , wherein the method is selected from the group consisting of: The at least one alkaline hydrolyzable group H-3 is selected from the group consisting of imidazole group, benzimidazole group, triazole group and benzotriazole group, and the at least one alkaline hydrolyzable group H-4. 7. The method of claim 6 , wherein is selected from the group consisting of succinimide groups and phthalimido groups.